4 naphthalimido pyrazolium salts

ABSTRACT

CATONIC ORGANIC COMPOUNDS ARE PROVIDED OF THE GENERAL FORMULA:   1,3-DI(O=),2-((+)B-),6-(R-O-)-2,3-DIHYDRO-   1H-BENZ(DE)ISOQUINOLINE A(-)   IN WHICH R REPRESENTS AN ALKYL RADICAL,B$ REPRESENTS A CYCLOAMMONIUM GROUP AND A REPRESENTS A MONOVALENT ANION. THESE COMPOUNDS CAN BE USED AS FLUORESCENT BRIGHTENING AGENTS FOR FIBRES BASED ON ACRYLONITRILE POLYMERS OR COPOLYMERS. A PROCESS FOR THE PREPARATION OF THE CATIONIC ORGANIC COMPOUNDS IS ALSO PROVIDED.

3,649,633 4 NAPHTHALIMIDO PYRAZOLIUM SALTS Georges R. H. Mingasson, Paris, and Annick M. S. S.

Domergue, Eaubonne, France, assignors to Ugine Kuhlmann, Paris, France No Drawing. Filed Aug. 9, 1968, Ser. No. 751,349

Claims priority, application France, Aug. 11, 1967,

117,728, Patent 1,541,050 Int. Cl. C07d 49/20 US. Cl. 260281 4 Claims ABSTRACT OF THE DISCLOSURE Cationic organic compounds are provided of the general formula:

in which R represents an alkyl radical, B represents a cycloammonium group and A represents a monovalent anion. These compounds can be used as fluorescent brightening agents for fibres based on acrylonitrile polymers or copolymers. A process for the preparation of the cationic organic compounds is also provided.

The present invention concerns new optical bleaching agents, their preparation and their applications.

The agents of this invention are novel cationic organic compounds which can be used as fluorescent brightening agents for fibres based on acrylonitrile polymers or copolymers and they are derivatives of naphthalic anhydride corresponding to the general formula:

in which R represents an alkyl radical, B represents a cycloammonium group and A represents a monovalent anion.

The radical R is preferably an alkyl radical containing from 1 to 4 carbon atoms for example, methyl, ethyl, propyl or isopropyl groups. These radicals may be sub stituted by at least one non-chromophore and non-anionic substituent such as for example a hydroxy or alkoxy group.

-By cycloammonium group is meant a monoor polycyclic heterocyclic group containing one or more hetero atoms, the hetero atom or one of the hetero atoms being a quaternary nitrogen atom. Examples of such groups are pyridinium, irnidazolium, pyrazolium, triazolium, thiazolium, oxazolium, oxadiazolium, thiadiazolium, quinolium and indazolium rings. These rings may be substituted by at least one non-chromophore and non-anionic substituent.

The cationic organic compounds of the invention are salts which are soluble in water, and their aqueous solu- United States Patent 3,649,633 Patented Mar. 14, 1972 "ice tions show an intense green-blue fluorescence. They have a good affinity for synthetic fibres based on acrylonitrile polymers or copolymers, with which they form true compounds, the cations being attached at the negative positions of the fibre. They impart to the acrylic fibres a remarkable effect of whiteness which persists on repeated washing and is stable to light and steaming and fast to chlorine.

Alkoxylated derivatives of naphthalimides are already known. Anselm and Zuckmeyer (Ben, 1899, 32, p. 3291) have prepared 4-methoxy-N-methylnaphthalimide. Similarly French Pats. Nos. 1,322,849 and 1,344,883 and US. Pat. No. 3,310,564 describe 4-alkoxy-naphthalimides in which the nitrogen atom is substituted by hydrocarbon radicals. These substances are insoluble in water, which makes their application complicated owing to the fact that they have to be very finely dispersed. Those which have a fluorescent brightening action on acrylic fibres owe it to absorption by the fibre, but not to a true chemical combination with the latter.

The compounds of Formula I can be prepared for example by reacting an alkylating agent of formula A-alkyl wherein A has the meaning given above, for example,

an alkyl halide, sulphate or sulphonate, with a compound of the general formula:

N B 0%; (7o Oi) in which R has the meaning given above and B represents a heterocyclic, monoor poly-cyclic group containing one or more atoms of nitrogen or one or more heteroatoms one of which is a nitrogen atom, possibly in the presence of a solvent such as for example an aromatic hydrocarbon or a chlorinated derivative thereof, an alcohol or dimethyl formamide. The preferred alkylating agent is an alkyl sulphate such as, for example, methyl sulphate. The compounds of Formula II may be obtained for example by any of several known processes, for example by the condensation of a 4-alkoxy-naphthalic anhydride, and especially 4-methoxy-naphthalic anhydride (C. 1926,

II, p. 2817-]. Chem. Soc. 1939, p. 792), with a hetero cyclic primary amine of the formula:

l3--NH in which B has the meaning given above.

It is also possible to prepare the compounds of Formula II from 4-bromo-naphthalimides of the formula:

and Pexton (J. Chem. Soc., 1954, p. 4435). This condensation is preferably carried out in a solvent such as for example water, alcohol or hydrocarbon, at a temperature between 100 C. and 200 C. Ethylene glycol and diethylene glycol, which can be used in a very wide range of temperature, are particularly suitable solvents. The bro- 4 NAPHTHALIMIDES OF FORMULA IV Example 1 14 parts of 4-bromo-naphthalic anhydride are conmonaphthalimides of Formula IV can then be converted 5 den-56d With Part5 P3f in 100 Parts of into alkoxynaphthalimides of the Formula II, owing to ethylene glycol y heahng the h f f hours at the mobility of the bromine atom. This property is pointed 1 After C001l11g3 the Pfeelpltate 1S filtered out by Graebe (Liebigs AHIL, 327 p. 87 and by Bradley w d with water a dned- Parts of f and Pexton (I. (Ihem. Soc., 1954, p. 4434 For this -py y p meltmg at 247-248 are conversion the bromonaphthalimides of Formula IV may obtained, of the formula: be treated in an. excess of alcohol ROH at the boiling point or under pressure with an alkali metal alcoholate N of formula ROMe, in which R has the meaning given 6 go above above and Me is an alkali metal, preferably sodium. l l

The quaternary salts of Formula I are very soluble in A Water, and their solutions are extremely fluorescent in I daylight and still more under the influence of ultraviolet rays. They may be applied to fibres based on acrylonitrile I polymers or copolymers such as those sold under the 13; trade names Orlon, Courtelle, Crylor, or Dralon, Ex 1 2 either by dyeing in a bath having a pH of from 4 to 7 amp 6 y any ether P f as for e e A mixture of 27 parts of 4-amin0-3,S-dimethyl-pyrazfixation or incorporation in the mass during spinning. A 016, 65 parts f 4 br0monaphtha1ic anhydride and 5 Very ehleh alhehht of theprodhet, of the eljder'ef to parts of water is boiled under reflux for 5 hours. It is 0.4% is sufiicient to obtain an excellent whitening effect. then left to cool, and the precipitate is filtered ff Washed The naphthalimides of the Formulae II or IV are new with water and dried. 83 parts f 3 5 compounds h for the most P they have e h methyl 4 pyrazolyl)-naphthalimide, melting at 267 0, cent properties and an aflimty for fibres which 15 too are obtained, f the f l small to have an optical bleaching efiect of any interest. In these circumstances it was unexpected that the conversion of the naphthalimides of Formula II into their CD quaternary derivatives would considerably increase the BI fluorescence of these compounds. 0 0/ The following Examples 1 to 61 illustrate the prepara- C-NH tion of these intermediate products. Examples 62 to 84 Ha illustrate the preparation of cycloammonium derivatives of naphthalimides according to the invention. Examples 011 replacing the Z-aminopyridine in Example 1 with 85 and 86 illustrate the use of the cycloammoniurn derivaother heterocyclic amines B'-NH and operating in a tives on acrylic fibres. These examples are purely illussimilar way, the following bromo-naphthalimides are trative and the parts given are parts by weight. obtained:

Example BNH: Naphthallmides 0! Formula IV M.P. C.

3 8-am1nopyrldlne 4-bromo-N-(3-pyrldyl)-uaphthalimlde 217 4 Z-amlno-fi-methyli-broruo-N-(ti-methyl-2-pyrldyl)- 238 pyridine. naphthalimide. 5 2-am1nothlazole 4-lilrlpiniio-N-(2-thlazolyD-naphthal- 298 8. 6 2-amino-4-methyl- 4-bromo-N-(4-methyl-2-thlazolyD- 248 thiazole. naphthalimlde. 7 Z-amlno-benzothlazole... 4-lggorlriizg-iNd-(2-benzothlazolyl)-naph- 300 8 6-arnlno-2-phenyl- 4-br mo-N32-phenyl-6-benzothla- 308 benzothiazole. zoly1)-naphthal1mlde. 9 4-amino-2-phenyl- 4-brozno-N-[4-(2-benzothlazolyl)- 326 benzothiazole. phenyH-naphthalimide.

10..-- 2-amlno-benzoxazole kbrolllih-ilg-fl-benzoxazolyl)-naph- 285 8 11 5-amin0-3-methyl- 443rorno-N (3-methyl-5lsoxazolyl)- 295 isoxazole. naphthalimlde. 12 6-amln0-2-methyl- 4-bromo-N-(2-methyl-6-quinolyl)- 287 quinollne. naphthalimlde. 13 2-amino-benzlmldazole..- i-BiOlilfifi-(Z-beDZlmldBZOlYD-Ilaph- 335 14 6-amlno-L2-dlmethyl- 4-br mo-N i1,Q-dImethyl-fi-benz- 32a benzimidazole. lmldazolyD-naphthallmlde. l5 4'-amln0-2phenyl- 4-bromo-N-[4-(Z-benzlmidazolyl)- 320 benzlmidazole. phenyH-naphthalimide. lfi. 4-amlno-2-phenyl-1- 4-bromo-N-[4-(1-methyl-2-benzlmida- 273 mgthyl-benzlmldazolyl)-phenylI-naphtha11mide. Z0 8. 17.-. 6-am1no-lndazole -lirlrldrlo-N-(ti-lndazolyl)-naphthal- 305 8. l8 3-amln0-6-chlorolnda- -bromo-N-(6-chloro-3-lndazolyD- 325 zole. naphthalimlde. 19 2-amlno-5-methyl-thlo- 4-bromo-N-(fi-methylthlo-2-thladla- 240 thladlazole. zolylynaphthnlimlde. 20 3-amino-4-phcnyl- -bromo-N-(4-phenyl-3 pyranzolyl) 298 pyrazolyl. naphthalimide.

TABLE.Cntinue(l Example B-NH Naphthallmldes of Formula IV M.P. C.

21..-- 3-amlno-5- henyl-pym- 4-bromo-N-(B-phenyl-B-pyrazolyl)- 286 zole. p naphthallmide.

22 3-amino'5-methy1-4- 4-bromo-N-(5-methy1-4-phenyl-3- 302 phenyl-pyrazole. pyrazolyD-naphthallmide.

23 4amino-3-methyl-5 4-bromo-N-(3-rnethyl-5-phenyl-4- 254 phenyl-pyrazole. pyrazolyD-naphthallmide.

24 4'-arnino-1-phenyl-3,5- ibromo-N-[4-(3,5-dimethyl-1-pyra- 245 dlmethyl-pyrazolo. zolyl)-phenyl]-naphthallmide.

25 4amlno-1-phenyl-3,5,5- 4-bromo-N-[4-(3,6,5-trirnethyl-1-A2- 238 trimethyl-A2-pyrazopyrazollnyl)phenyH-naphthalline. imide.

26 3-am1no-1,2,4-4H-tri- 4-bromo-N-(1,2,4-4H-triazol-3-yl)- 350 azole. naphthallmlde.

27 3-amJn0-5- henyl-l,2,4- 4-bromo-N-(5-phenyl-l,2,4-4H-trlazol- 345 4H-triazole. 3-yl-naphthalimide.

28 4-am1no1,2,4-4H- 4-bromo-N-(1,2,4-4H-trlazol-4-y1)- 350 trlazole. naphthalimide.

29 4-amlno-3-phenyl-6- 4-bromo-N-[4-(5-methyl-1,2,4-4H- 300 methyl-1,2,4-4IL phenyH-naphthallmide. trlazole.

NAPHTHALIMIDES OF FORMULA (II) Example 53 Example 4 parts of sodium are dissolved in 250 parts by volume of methyl alcohol in an apparatus provided with a stirrer and a reflux condenser. Then 14.12 parts of 4-bromo- -N-(2pyridyl)-naphthalimide are added and the mixture is heated under reflux for 3 hours. The reaction mixture thickens and becomes a pale yellow colour. After cooling, the precipitate is filtered off, taken up in dilute acetic acid, filtered and washed with water, then With alcohol. After drying, 11.3 parts of 4-methoxy-N-(2-pyridyl)- A mixture of 11.4 parts of 4-methoxy-naphthalic anhydride with 4.7 parts of 2-aminopyridine and 100 parts of ethylene glycol is heated for 6 hours at ISO-160 C. with stirring. After cooling, filtering off the precipitate, washing with alcohol and drying, 13 parts of a product similar to that from Example 30 are obtained.

On operating as in the preceding example, but replacing the Z-aminopyridine by equivalent quantities of the following heterocyclic amines the corresponding 4-methoxy-naphthalimides are obtained:

Example B-NH2 Naphthalimides of Formula II M.P. O

54 2-amino-benzothiazole... 4-methoxy-N(2 benzothiazolyl)- 220 naphthalimide. 55 6-amino-2-phenyl-benzo- 4-methoxy-N-(2-phenyl-6-benzothia- 350 thiazole. zolyl)-naphthalimide. 56 2-amino-benzoxazole 4-methoxy-N-(2-benzoxazoly1)-naph- 320 thalimide. 57 6-amino-2-phenyl-benz- 4-methoxy-N-(2-phenyl-6-benzoxa- 336 oxazole. z0lyl)naphthalimide. 6-amin0-2-methyl- 4-rnethoxy-N-(2-methyl-6-quinolyl)- 255 quinoline. naphthalimide. .59 2-amino-4-methyl- 4-methoxyN-(4methyl-2rquinolyl)- 262 quinoline. naphthalimide.

o napthahmide of melting point 240 C. are obtained. On Example 60 recrystallising from a mixture of alcohol and dimethyl 50 formamide, the product forms long yellow needles melting at 242 C.

By the application of the same process to the 4-brornonaphthalimides of Examples 2 to 29, the corresponding 4-methoxy-naphthalimides are obtained, the melting points of which are given below:

M.P. of the 4- methoxy derivative in C.

Example Initial -bromo-naphthallmlde 52 I Example 29 4 parts of sodium are dissolved in 200 parts by volume of anhydrous ethyl alcohol in a round-bottomed flask provided with a stirrer and a reflux condenser. 14.12 parts of 4-bromo-N-(Z-pyridyD-naphthalimide are added and the mixture is refluxed for 3 hours. After cooling, the precipitate is filtered 01f, washed with a little alcohol, then with water until the filtrate is neutral, and dried. 4- ethoxy-N-(Z-pyridyl)-naphthalimide of melting point 232 C. is thus obtained.

Example 61 On replacing the 4-bromo-N-(Z-pyridyl)-naphthalimide in the preceding example by 13.7 parts of 4-bromo-N- 1,2,4-4H-triazol-3-yl)-naphthalim.ide, 4-ethoxy-N-( 1,2,4- 4H-triazol-3-yl)-naphthalimide of melting point 338 C. is obtained.

NAPHTHALIMIDES O'F FORMULA (I) Example 62 10 parts of methyl sulphate are introduced into an apparatus provided with a stirrer and a thermometer and are heated to C. and 10 parts of 4-methoxy-N-(2- pyridyD-naphthalimide are then gradually introduced.

The temperature of the mixture is raised to 130 C. and this temperature is maintained for about an hour, until a sample taken is completely soluble in water. The product is allowed to cool, diluted with 50 parts of water and left with stirring to decompose the excess methyl sulphate. It is then boiled with a little decolorising charcoal and filtered. After cooling, 10 parts of sodium chloride are added to the filtrate, then a dilute solution of zinc chloride, until precipitation is complete. After filtering and drying the precipitate, 12 parts of the chlorozincate of 4'-methoxy-2-naphthalimido l methyl-pyridinium monohydrate are obtained. After recrystallising from water, analysis gives the following figures:

Calculated for C H N O Cl+- /2ZnCl -l-H O (percent): C, 51.8; H, 3.86; N, 6.36; Cl, 16.1. Found (percent): C, 51.96; H, 3.90; N, 6.70; Cl, 16.7.

This product is in the form of a light beige crystalline powder, and is very soluble in water. Its dilute aqueous solutions show an intense blue fiuoroescence.

Example 63 5.2 parts of 4 methoxy N (2-benzimidazolyl)-naphthalimide are disolved in 25 parts of dimethyl formamide. 3 parts of methyl sulphate are added and the mixture is heated at 130 C. until a sample is soluble in water. After cooling, 50 parts of water are added, the product is boiled with a little decolorising charcoal and filtered. Sodium chloride is added to the filtrate. A light yellow crystalline product is precipitated. parts of 4'-methoxy-2-naphthalimido-l,3-dimethyl-benzimidazolium chloride are thus obtained. After recrystallisiug from water, analysis gives the following results:

Calculated for C H N O Cl, H O percent: C, 62.06; H, 4.7; N, 9.87. Found percent: C, 61.7; H, 5; N, 9.49.

This compound gives extremely fluorescent aqueous solutions.

Example 64 8 parts of 4-methoxy-N-[4-(3,5-dimethyl-1-pyrazolyl)- phenyl]-naphthalimide (Example 47) are heated under reflux in 100 parts by volume of chlorobenzene and 5 parts of methyl sulphate are introduced in a period of an hour. The mixture is boiled for 2 hours and the solvent is removed by steam distillation. The solution is treated with carbon black, filtered, then cooled. The chlorozincate of 4"-methoxy-4'-naphthalimido-1-phenyl-2,3,5-trimethylpyrazolium is precipitated by the addition of salt and a solution of zinc chloride.

Example 65 3 parts of 4-methoxy-N-(1,2,4-4H-triazol-4-yl)-naphthalimide from Example 51 are gradually introduced into 5 parts of ethyl sulphate heated to 130 C. This temperature is maintained until a sample is soluble in water. The mass is dissolved in water. The solution is boiled with decolorising charcoal, filtered and sodium chloride and zinc chloride are added to the cooled solution. 4'-methoxy- 4- naphthalimido-l-ethyl-(or 2-ethyl)-triazolium chlorozincate is thus obtained in the form of a light yellow powder which is soluble in water with an intense blue fluoroescence.

Examples 66 to 84 On operating in a similar Way according to one of the processes described in Examples 62, 63 and 64 the salts (chlorozincate or methyl sulphate) of other cycloammonium derivatives of Formula I are obtained from 4- alkoxy-naphthalimides of Formula II and previously described.

Naphthalimide of Formula 11 of Example:

lit

Example A treatment bath is prepared with 3000 parts of water, 3 parts of acetic acid .and 0.4 part of the benzimidazolium, salt of Example 63. It is heated to 40-50 C. and parts of an Orlon fabric are introduced. The bath is heated to boiling and maintained at this for an hour. The fabric is removed, rinsed and dried. It has attained a remarkable whiteness. The same elfect is obtained on a fabric where the Orlon fibres have been replaced by Courtelle, Crylor or Dralon fibres.

Example 86 The operation is carried out exactly under the conditions described in Example 85, but 5 parts of sodium chlorite have been previously added to the bath. The optical bleaching effect observed is still more intense.

We claim:

1. Compound of the formula:

de y

in which R is an alkyl radical, or a hydroxy or alkoxy substituted alkyl radical, said alkyl having one to four carbon atoms, X is a direct linkage or p-phenylene, B is an N -(lower alkyl) cycloammonium group in which the cycloammoniurn group is pyrazolium and is attached to X through a carbon atom, the remaining carbon atoms in pyrazolium being unsubstituted or substituted by chlorine, lower alkyl, phenyl, or methylthio groups, and A is a colorless monovalent anion.

2. Compounds according to claim 1 wherein R is a methyl, ethyl, propyl or isopropyl group.

9 l0 3. The salts of 4'-methoxy-3-naphthalimido-4-phenyl FOREIGN PATENTS 1,2-dimethyl-pyrazolium in which the anion is a colourless 14 988 7/1964 Japan moHOvalent anion- 27127 11/1964 J 260 2s1 4. Th6 salts of 4' -rnethoxy- 4-naphthalimido-l,2,3,5- 1 tetramethyl-pyrazolium in which the anion is a colourless 5 monovalent amon- DONALD G. DAUS, Primary Examiner References Cited CL UNITED STATES PATENTS s ss; 252 301.2 w; 260-288, 304, 305, 306.8, 307 D, 3,310,564 3/1967 Kaisai 260281 10 307 H, 308 R, 309, 309.2, 310 R, 310 D 3,330,834 7/1967 Senshu 260-281 

